Method of catalysis



April 1944- J. D. DANFORTH 2,346,294

METHOD OF CATALYSIS- Filed July 30, 1941 CYCZL ONE SEPA RH TOR g 5% wag 2% s m5 Q *1 M I 3 (:7 jHaz/ggg.

Patented Apr. 11, 1944 2,346,294 METHOD or CATALYSIS Joseph D. Danforth, Chicago, 111.,

Universal Oil Products Company,

assignor to Chicago, 111.,

a corporation of Delaware Application July 30, 1941, Serial No. 404,603

'(Cl. 260-683A) 14 Claims.

This invention relates to a novel 'method of catalysis. 'More specifically the invention is'concemed with a process for efiecting chemical reactions in the presence of a catalyst introduced by means of afluid carrying medium to a reaction zone containing a catalyst supporting material freely dispersed throughout the reactants.

In my co-pending application Serial No. 370,323, filed December 16, 1940, I have described a process for effecting hydrocarbon reactions in the presence of a catalyst introduced by means of a fluid carrying medium to a reaction zonecontaining a packing material. In said process the packing material was in the form of a fixed bed and was either adsorptive or non-adsorptlve. However, the use of an adsorptive support in a fixed bed process has a certain disadvantage in that any adsorptive surface tends to become fouled with contaminating materials and the surface no longer adsorbs the fresh catalyst entering the reaction zone. When this occurs it is necessary to reactivate the adsorptive surface in some manner, and this usually means, in a continuous process, that periodically a reactor must be withdrawn from service for reactivation. This cycle of operation necessitates more rigid control and requires the installation of additional equipment to carry out the reactivation of the adsorptive support. In the process of the present invention I continuously add to and remove from the reaction zone portions of the adsorptive solid supporting material and also separately add, a catalyst to the stream of reactants. In the reaction zonethe catalyst is'adsorbed or deposited on the surface of the freely dispersed supporting material.

One specific embodiment of the present invention comprises passing a stream of fluid reactants to. a hindered settling type reactor wherein the stream of reactants passes upwardly througha a bed of freely dispersed solid catalyst-supporting particles at such a rate that the catalyst particles are maintainedin a state of constant agitation but the major portion of said particles are not carried out of the reaction zone, continuously adding a relatively small proportion of inert solid adsorptive particles to the reactants prior to the reaction zone, separately addin a streamof fluid catalysts to the stream of reactants prior to the reaction zone, controlling the addition of the fluid catalyst so that substantiallyall of the catalyst is adsorbed on the surfaceof the solid adsorptive particles in the reaction zone,- withdrawing a stream of reaction products from the reaction zone together with a small proportion oi the solid particles supporting partially spent catalyst, and

separating said solid particles from said reaction products in a separation zone.

A hindered settling type reactor as mentioned in this specification indicates any type of reactor in which a stream of fluid reactants pass upwardly through a bed of finely divided solid particles at such a rate that said particles are maintained in a state of agitation but a major proportion of which are not carried out of the reaction zone with the reactants.

By the process of the present invention catalytic materialsuch as aluminum chloride may be introduced to a reaction zone by means of one or more fluids being charged'thereto. Thus either a portion or all of the reactants or a fluid such as gaseous hydrocarbons which is substantially inert toward the catalyst may be passed through a chamber containing the catalyst at a temperature and pressure which enables the catalyst to be vaporized or dissolved in a. sufiicient amount. The resulting catalyst laden stream of fluid is then mixed with the rest of the charge to the reaction zone comprising reactants and/or'a minor proportion of finely divided substantially inert adsorptive solid and the mixture is admitted to said reaction zone which contains a substantial proportion of said finely divided inert solid freely dispersed therein. The freshly added catalyst de posits on the surface of said finely divided inert solid to form a supported aluminum chloride catalyst. A small amount of hydrogen chloride is also preferably added to the reactant stream to activate the aluminum chloride catalyst. Since the adsorptive surface of the inert support will eventually become inactive, it will be necessary to remove and reactivate a portion of the finely divided particles. This is most easily accomplished by regulating the flow in the reactor so as to carry a portion of the finely divided supported catalyst out of the reactor with the conversion products. This partially spent catalyst is separated from the conversion products and then the inert support may be reactivated by any one of several methods.

One method of reactivation involves heating the spent catalyst to drive off volatile matter including unused catalyst and subsequently oxidizing the carbon deposit left after the devolatilization in a stream of hot oxygen-containing gaSeS- Another method of reactivating the inert supporting material is to contact the material with a stream of live steam. This steaming operation may also. conveniently be carried out in a hindered settling type of oontactorq After reactivacatalyst.

tion of the adsorptive surface of the inert supporting material it may be again introduced to.

the reactant stream prior to the reaction zone or directly to the reaction zone. The surface of the finely divided. supporting material need not be adsorptive in all cases. For instance, in'the alkylation of iso-paraflins with oleflns using an vated char. The above mentioned catalysts and supports are not necessarily equivalent in their suitability for use in the process of this invention.

The addition of volatile catalysts tothe reactants separately from the finely divided sup porting material has "a distinct advantage. If the catalysts were adsorbed on the solid supporting material prior to their introduction ,to the reactant stream, the amount of catalyst introduced to the system would be limited to the amount of catalyst adsorbed on the portion of finely divided solid particles being added to the reactants. It would not be possible to renew the catalyst layer on the surface of the large quantity of finely divided catalyst suspended in the. reaction zone. The volatile catalyst adsorbed on the surface of the support is not equilibrium with the catalyst in the fluid phase of the reactants and, therefore, if no method of adding fresh catalyst is provided the catalyst adsorbing surface of the support in the reaction zone will gradually become impoverished.

high and is only limited by the requirement that the material remain in a fluid state.

The stream of reaction products leaving the reactor will carry approximately the same amount of finely divided solids as the entering stream of reactants. This finely divided solid material which will have a certain amount of active and/or spent catalyst adsorbed on its surface will be separated from the conversion products ordinarily by some mechanical or electrical precipitation method and may then .be reacti vated in some suitable manner such as by oxida- In the process of this invention the catalyst is introduced to the reaction zone separately from the adsorptive supporting material and therefore can be introduced in any amount that is necessary to maintain the activity of the sup- Ported catalyst at a desired level.

In a hindered settling catalytic process the catalyst or, as in the case of this invention, the catalyst and its support is usually added with the charge. The ratio of the amolmt of finely divided solid particles to the amount of reactants in the charge to the reaction zone will vary widely depending on the life of the solid catalytic material before reactivation is necessary. Generally, however, the above-mentioned ratio will be much less than the corresponding ratio in the reaction zone. The mixture of reactants, catalysts, and catalyst support, is introduced to the reactionzone where the reactants pass upwardly through a bed of freely dispersed finely divided solid particles carrying the adsorbed The concentration of finely divided solid particles in the reaction zone will also vary depending upon the rate of flow, particle size,

etc., but in any case will be much higher than in the incoming stream of reactants. This higher tion, hydrogenation, steaming, washing, etc.v ancb returned to the stream ofreactants entering the reactor. It is not always necessary to remove all of the adsorbed catalytic material from the finely divided adsorbent solid particles in the reactivation step as, in some instances, a partial reactivation of the adsorptive surface will. be sufllcient. The recycled solid adsorptive particles will in this case contain some active catalyst adsorbed thereon prior to contact with the liquid. phase the catalyst may be introduced either as a solution of the catalyst in the liquid charge, for instance, a solution of aluminum chloride in a liquid hydrocarbon, a separate immiscible liquid or a gaseous material composed in part or entirely of vaporized catalyst. If the reactants are in the vapor phase the catalyst-will usually also be in the vapor phase, although the invention is not so limited. v

The accompanying drawing diagrammatically illustrates one way in which this invention may be employed in a catalytic process.

Referring to the drawing, a stream or fluid reactants enters-through line I valve 2, and pump 3 into line 4 where it is separated into two streams. One stream passes through valve 5 after which the finely divided inert adsorptive particles are added to the stream. The finely divided inert particles are stored in a feed tower 6 which is of sumcient height to provide the necessary pressure to force them through valve 1- 1 other. reactant stream'containing finely divided concentration is possible because the solid catalyst-supporting particles which are 'more dense than the reactants tend to settle out against the upward flowing stream of reactants. In the stream of, reactants prior to the reaction zone the velocity is kept high enough to prevent any appreciable settling out of the solid particles. The concentration of the solid catalyst'supportadsorbent particles in line 4. The combined re-' actant streams flow through line 4 and valve It to reaction zone l1. Inreaction zone I! a high concentrationiof finely divided adsorbent particles is attained by an increase in the cross-section of the flowing reactant stream suiflcient to allow the solid particles to' settle against the upwardly flowing stream of reactants; The catalyst added to the stream in pickup chamber l3 'being particles in the reaction zone may be very comes adsorbed on the finely divided adsorptive 70.

particles in line 4 and in reaction zone H. The

reaction products and a portion of the finely divided particles with adsorbed catalyst pass through lint? i8 and valve is to cyclone separator 20 wherein the fluid reaction products and the finely divided solidparticles are separated. The

either the liquid reaction'pronucts are withdrawn through line Z-l and valve 22 and the finely divided solid particles settle out and are withdrawn through valve 23 and line 24.

The catalytic isomerization oi parailin hydrocarbons to produce branched chain hydrocarbons or more highly branched chain hydrocarbons with an aluminum chloride catalyst may be accomplished advantageously by employing the process of this invention. The paraflincharge may be either butane or normally liquid parafiins such as pentane, hexane or heptane or may even be a low boiling gasoline fraction. The reaction may be carried out either in the liquid or vapor phase at a temperature between 100 and 500 F.

Suitable powdered adsorbents include alumina, bauxite-activated char; acid treated clays, etc. All or a portion of the charge may pass through an aluminum chloride pickup chamber containing granular aluminum chloride. The catalyst laden stream is then combined with the stream containing the finely divided adsorbent and the combined streams passed to the reaction zone. A small amount of dry hydrogen chlorideds also preferably added to the reaction zone to activate the aluminum chloride catalyst.

The catalytic alkylation of iso-parafiins with olefins to produce saturated branchedchain hydrocarbons of high octane ratingmay also be carried out by employing the method of catalysis as shown by this invention. An aluminum chloride-hydrogen chloride catalyst may be used in conjunction with various powdered supports such as alumina, activated char, porcelain, clay, quartz, etc. Another catalyst which may be .used for alkylation is hydrogen fluorid e. This catalyst is a liquid boiling at about 20 C. under atmospheric pressure.' In the process of this invention this catalyst may be introduced to the process in or vapor phase and may be used in conjunction with 'a non-reactive finely divided supporting materialsuch as' activated char. The above alleviation processes may be carried out using the normal or superatmospheric pressures and at temperatures of about F. to about 250 F. 4

Other processes which may use the method oi catalysis as shown by this invention will 'include the catalytic cracking of hydrocarbons usin either an aluminum chloride catalyst or a boron fluoride catalyst and a suitable inert supporting material or the catalytic reforming of a gasoline or naphtha employing one of these catalysts. Y

The following illustrative example is given to indicate how the present invention may be applied to an isomerization process:

' Example A stream of liquid normal butane charging stock heated to 180 F., is divided into equal portions. To one stream is added approximately 4% by weight of finelydivided alumina, while the other stream is passed through a chamber containing granular aluminum chloride which dissolves in the charging stock; The aluminum chloride-containing streamwill contain approximately 1% aluminum chloride by weight. The two streams ofichargihg stock are then combined and directed'to a reaction zone where the combined stream containing aluminum chloride, finely divided alumina, and normalbutane is passed upwardly through a freely dispersed bed of finely divided alumina. supporting aluminum chloride catalyst. The ratio of fln'ely divided solids to'reactants in the reaction zone is greater than one.

The reaction products carrying a small proportion of finely divided supported catalyst, are withdrawn to a separator where thesolid particles settle out. The reaction products con train 47% isobutane and the remainder essentially normal butane.

While the foregoing specification and illustrations are indicative of the character of the invention, it is not intended that the broad nature of the invention should be limited by the specific applications indicated therein.

I claim as my invention:

1. In a process for effecting chemical reaction wherein a stream of reactants is passed through a reaction zone containing solid particles maintained in a state oi motion in the reaction zone, the method which comprise intro- 0 ducing. an additional quantity of said particles .to the reaction zone by adding the same to the reactant stream being supplied to said zone, simultaneously introducing to the reaction zone an unsupported catalyst for said reaction, and depositing the catalyst on "the solid particles within the reaction zone.

2. The process asdefined in claim 1 further characterized in that said unsupported catalyst is introduced to the reaction zone with a portion of ,the reactants being supplied to the reaction zone.

3. In a process for eflecting chemical reaction wherein a stream of reactants is passed through a reaction zonecontaining freely dispersed, solid particles maintained in astate of agitation in the reaction zone, the methQd which comprises dispersing an additional quantity of said particles in a portion of the reactants. to be supplied to the reaction zone, dispersing ,a catalyst forsaid reaction in another portion of the reactants, simultaneously introducing said portions of the reactants to the reaction zone, depositing the catalyst on the solid particles within the reaction zone, and removing from said zone .a stream of reaction products containing an amount of said particles which is relatively small with respect to that present in the reaction zone.

4. The process as defined in claim 1 further characterized in that said particles are adsorptive and the catalyst deposited thereon by adsorption.

5. The process as defined in claim 3 further characterized in that said particles are adsorptive and the catalyst deposited thereon by adsorption.

, 6. In the conversion of hydrocarbons wherein -a stream of hydrocarbon reactants is passed through a reaction zone containing solid par-- ticles maintained in a state of motion in the reaction zone, the method which comprises introducingan additional quantity of said par-' ticles to the reaction zone by adding the same to the hydrocarbon reactant stream being supplied to said zone, simultaneously introducing to the reaction zone an unsupported catalyst for the conversion reaction, and depositing the catalyst on the solid particles within the reaction zone.

7 The process as defined in claim 6 further characterized in that said unsupported catalyst is introduced, to the reaction zon with a portion of the reactants being supplied to the re-' action zone.

8. In the conversion of I hydrocarbons wherein reactants,. passing another portion oi the re actants through a body oi aluminum chloride to disperse aluminum chloride therein, simultaneouslyintroducing said portions of the reactants to the reaction zone and therein depositing the aluminum chlorideon the solid particles.

9. In the conversion of hydrocarbons in a reaction zone containing finely divided solid particles' maintained in a stateot motion within the reaction zone, the method which comprises dispersing an additional quantity of said particles in a portion ,of thehydrocarbon reactants to be supplied to the reaction zone, dispersing a catalyst for said reaction in another portion of the reactants, simultaneously introducing said portions of the reactants to the reaction zone',depositing the catalyst on the solid particles withinjhe reaction zone, and removing from said zone a stream of reaction products containing an amount of said particles which is relatively small with respect to that present in the me tion zone.

10. The method as isifflned in claim a further characterized in that id catalyst comprises'an aluminum halide.

11. In the conversion of hydrocarbons in a reaction zone containing finely divided solid par. ticies maintained in a state of motion within the reaction zone, the method which comprises dis solving an aluminum halide inla liquid portion of the hydrocarbon reactants to be s pplied to said zone, adding finely divided solid particles to another portion of the reactants to be supplied to the reaction zone, simultaneously introduc asi e ing said portions or the reactants to said zone and depositing the aluminum halide on the solid particles within the reaction zone.

' 12. In the conversion of hydrocarbons in a reaction zone containing finely divided solid in a state of motion within reaction zone, the method which comprises adding finely divided solid particles to a hydro-l carbon reactant stream to be supplied to the reaction zone,- then adding an unsupported catalyst for the conversion reaction to said stream and promptly thereafter introducing the composite stream to the reaction zone, and depositin: the catalyst on the solid particles within said zone.-

K13. In the alkylation of an alkylatable hydrocarbon with ,an oleiinic hydrocarbon in a reaction zone containing finely divided solid particles maintained in a state of motion within the reaction zone, the method which comprises introducing an additional quantity of said particles to the reaction zone by adding the same to a stream of hydrocarbon reactants being supplied, to said zone, simultaneously introducing unsupported aluminum chloride to the reaction zone and depositing the aluminum chloride on the 14. In the isomerization of parafllnic hydrocarbons in a reaction zone containing finely divided solid particles maintained in a state of motion within the reaction zone, the method which comprises introducing an additional quantity oi said particles to the reactionzon'e by adding the same to a stream'oi paramnic hydrocarbons being supplied to said zone, simultaneously introducing unsupported aluminum chloride to the reaction zone and depositing the' aluminum chloride on the solid particles within said zone.

JOSEPH D. DANFORTH: 

